TWI392769B - Rinsable metal pretreatment methods and compositions - Google Patents

Rinsable metal pretreatment methods and compositions Download PDF

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TWI392769B
TWI392769B TW095101228A TW95101228A TWI392769B TW I392769 B TWI392769 B TW I392769B TW 095101228 A TW095101228 A TW 095101228A TW 95101228 A TW95101228 A TW 95101228A TW I392769 B TWI392769 B TW I392769B
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acid
group
phosphonic acid
phosphonate
composition
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TW200643222A (en
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Edward A Rodzewich
Jeffrey I Melzer
Philip D Deck
Whisenhunt, Jr
William S Carey
David B Engel
Bret Chisholm
Christopher M Carter
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Chemetall Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Description

可沖洗的金屬預處理方法及組合物Flushable metal pretreatment method and composition

本發明係關於用於金屬之不含鉻塗層。更特定言之，本發明係關於用於鋼、鍍鋅鋼、及鋁之表面之可沖洗、無鉻酸鹽、無金屬磷酸鹽之塗層以改良乾燥塗層至該表面之附著並提供增強的防腐蝕作用。This invention relates to chromium-free coatings for metals. More particularly, the present invention relates to washable, chromate-free, metal-free phosphate coatings for steel, galvanized steel, and aluminum surfaces to improve adhesion of dry coatings to the surface and provide reinforcement Anti-corrosion effect.

在金屬表面採用鉻酸鹽或磷酸鹽轉化塗層或鈍化塗層以給予裸金屬及經塗佈之金屬之經改良的耐蝕性，改良塗層之附著力，並用於審美目的，此對熟習此項技術者係熟知的。例如，參見Corrosion ,L.L.Sheir,R.A.Jarman,G.T.Burstein,Eds.(第三版，Butterworth－Heinemann Ltd,Oxford,1994)，第二卷，第15.3章。The use of a chromate or phosphate conversion coating or passivation coating on the metal surface to impart improved corrosion resistance to bare metal and coated metal, improved adhesion of the coating, and for aesthetic purposes, The skilled person is well known. See, for example, Corrosion , LL Sheir, RA Jarman, GT Burstein, Eds. (Third Edition, Butterworth-Heinemann Ltd, Oxford, 1994), vol. II, Chapter 15.3.

關於鉻的毒性概況以及鉻酸鹽、磷酸鹽及藉由該等製程排入河流及水道的其它重金屬之污染影響，吾人擔心日益增加。由於六價鉻離子之高溶解性及強氧化性特徵，習知鉻酸鹽轉化製程需要大量的水處理程序以控制其排出。磷酸鹽製程亦需要在排出之前的廢物處理程序。另外，處理來自該等廢物處理程序之固體污泥為一重要問題。With regard to the toxicity profile of chromium and the pollution effects of chromate, phosphate and other heavy metals discharged into rivers and waterways by these processes, we are increasingly concerned. Due to the high solubility and strong oxidizing characteristics of hexavalent chromium ions, the conventional chromate conversion process requires a large amount of water treatment procedures to control its discharge. The phosphate process also requires a waste disposal process prior to discharge. In addition, handling solid sludge from such waste treatment processes is an important issue.

因此，在此項技術中需要提供基於無鉻酸鹽、無金屬磷酸鹽、或減少的磷酸鹽之有效處理以抑制金屬表面腐蝕並增強可塗覆至該表面之油漆或其它塗層之附著力。Accordingly, there is a need in the art to provide an effective treatment based on chromate-free, metal-free phosphate, or reduced phosphate to inhibit metal surface corrosion and enhance adhesion of paints or other coatings that can be applied to the surface. .

提供酸性水溶液或分散液以與諸如鋼、鍍鋅鋼、及鋁之表面之必要的金屬表面接觸。該等溶液及分散液不含鉻酸鹽並提供金屬表面上經增強之防腐蝕作用及乾燥塗層之黏著性。此等乾燥塗層通常包括油漆、快乾漆、墨水、清漆、樹脂等。An acidic aqueous solution or dispersion is provided to contact the necessary metal surfaces such as steel, galvanized steel, and aluminum surfaces. These solutions and dispersions do not contain chromate and provide enhanced corrosion protection on the metal surface and adhesion of the dried coating. Such dry coatings typically include paints, quick-drying paints, inks, varnishes, resins, and the like.

本發明之方法包含將必要的金屬表面與有效量之酸性水性組合物或分散液接觸以增強防腐蝕作用及乾燥塗層之黏著性。不含鉻酸鹽及無機磷酸鹽之組合物或分散液包含(a)包括一IVB族元素之一或多種材料；(b)一氟化物源；及(c)膦酸或膦酸酯。將金屬表面與以上組合物或分散液接觸之後，可沖洗該塗層並在適當位置進行乾燥。隨後該表面便準備好在其上塗覆油漆、快乾漆、清漆、樹脂或其它乾燥塗層。The method of the present invention comprises contacting the necessary metal surface with an effective amount of an acidic aqueous composition or dispersion to enhance the corrosion protection and adhesion of the dried coating. The composition or dispersion containing no chromate and inorganic phosphate comprises (a) one or more materials comprising a Group IVB element; (b) a source of monofluoride; and (c) a phosphonic acid or phosphonate. After contacting the metal surface with the above composition or dispersion, the coating can be rinsed and dried in place. The surface is then ready to be coated with paint, quick-drying paint, varnish, resin or other dry coating.

本發明者已發現可在金屬表面尤其是鋼表面、鍍鋅鋼及鋁表面提供一經改良之無鉻酸鹽轉化塗層或鈍化塗層。此酸性水性組合物或分散液包含(a)包含選自如元素週期表CAS版中所列明之一或多個IVB族元素之一或多種材料。該等元素包含Zr、Ti及Hf。可包括此等元素之混合物。含有Zr及Ti之材料為較佳的。示範性Zr源經調適以於酸性介質中提供Zr陰離子且包括可溶性氟鋯酸鹽、氟化鋯(ZrF4 )、或諸如硝酸鋯或硫酸鋯之水溶性鋯鹽。另外，鋯源可包含銨鹽或鹼性鋯鹽。可使用氧化鋯及Zr金屬本身，只要其於酸性介質中電離為Zr陰離子。最佳地，Zr源包含氟鋯酸H2 ZrF6 。另外，含有機Zr之化合物若能在酸性水性介質中釋放出Zr則可利用含有機Zr之化合物。The inventors have discovered that a modified chromate-free conversion coating or passivating coating can be provided on metal surfaces, particularly steel surfaces, galvanized steel, and aluminum surfaces. The acidic aqueous composition or dispersion comprises (a) comprising one or more materials selected from one or more of the Group IVB elements as listed in the CAS version of the Periodic Table of the Elements. These elements include Zr, Ti, and Hf. Mixtures of these elements can be included. Materials containing Zr and Ti are preferred. Exemplary Zr Zr source adapted to provide an acidic medium comprises an anion and a soluble fluorozirconate, zirconium fluoride (ZrF 4), or water-soluble zirconium salt such as zirconium nitrate or zirconium sulfate. Additionally, the source of zirconium may comprise an ammonium salt or a basic zirconium salt. Zirconium oxide and Zr metal itself may be used as long as they are ionized into Zr anions in an acidic medium. Most preferably, the Zr source comprises fluorozirconic acid H 2 ZrF 6 . Further, if a compound containing a machine Zr can release Zr in an acidic aqueous medium, a compound containing an organic Zr can be used.

IVB族元素亦可包含Ti。較佳的Ti源為H2 TiF6 ，但諸如TiF3 及TiF4 之氟化鈦亦可被提及。硝酸鹽、硫酸鹽、銨鹽或鹼性鈦鹽以及Ti金屬本身亦可使用。另外，有機Ti化合物若能在酸性介質中釋放Ti則可使用有機Ti化合物。初步試驗包括使用異丙醇鈦(iv)作為Ti源組分，尤其在其與諸如H2 ZrF6 之酸性溶液反應之情況下。The Group IVB element may also contain Ti. A preferred Ti source is H 2 TiF 6 , but titanium fluoride such as TiF 3 and TiF 4 may also be mentioned. Nitrate, sulfate, ammonium or alkaline titanium salts and Ti metal itself can also be used. Further, an organic Ti compound can be used if the organic Ti compound can release Ti in an acidic medium. Preliminary tests included the use of titanium isopropoxide (iv) as the Ti source component, especially in the case of its reaction with an acidic solution such as H 2 ZrF 6 .

用作酸性處理液或組合物之組分的氟化物源(b)最佳地可為可用以提供Ti及/或Zr之同樣的氟鋯酸或氟鈦酸。最佳地，該處理液包含H2 ZrF6 與H2 TiF6 ，其組合將足以用作Zr、Ti及氟化物之來源。其它適當F源包括氫氟酸及其鹽、鹼金屬二氟化物、H2 SiF6 及HBF4 。此外，該源必須能在介質中釋放F。最佳地，經組合之Zr、Ti及F源在介質中釋放氟鈦酸根及氟鋯酸根，即(TiF6 )－ 2 及(ZrF6 )－ 2 。The fluoride source (b) used as a component of the acidic treatment liquid or composition may optimally be the same fluorozirconic acid or fluorotitanic acid which can be used to provide Ti and/or Zr. Most preferably, the treatment fluid comprises H 2 ZrF 6 and H 2 TiF 6 , the combination of which will be sufficient to serve as a source of Zr, Ti and fluoride. Other suitable F sources include hydrofluoric acid and its salts, alkali metal difluorides, H 2 SiF 6 and HBF 4 . In addition, the source must be able to release F in the medium. Most preferably, the combined Zr, Ti and F sources release fluorotitanate and fluorozirconate in the medium, namely (TiF 6 ) - 2 and (ZrF 6 ) - 2 .

所需的氟化物濃度為使該氟化物與Zr及Ti結合以與之形成錯合物之濃度，例如氟鋯酸鹽與氟鈦酸鹽。通常，每存在一莫耳Zr與Ti便提供至少約4莫耳氟化物。鋯及鈦可以高達略大於其溶解限度之量存在於處理介質中。The desired fluoride concentration is the concentration at which the fluoride combines with Zr and Ti to form a complex with it, such as fluorozirconate and fluorotitanate. Typically, at least about 4 moles of fluoride is provided for each mole of Zr and Ti present. Zirconium and titanium may be present in the treatment medium in amounts up to slightly above their solubility limit.

關於調配物之組分(c)膦酸及膦酸酯，此可敍述為包括為具有下式的任何化合物： 其中X為H或陽離子；R為包括下列基團的任何有機部分：烷基、環烷基、經取代及未經取代之含N及/或P之雜環、芳基、包括經鹵化芳基及烷基取代芳基之經取代芳基，諸如胺基烷基、羧烷基、膦酸基烷基、烷亞胺基、羥烷基、矽烷取代之烷基之經取代之烷基等。With regard to the components of the formulation (c) phosphonic acid and phosphonate, this can be described as including any compound having the formula: Wherein X is H or a cation; R is any organic moiety comprising an alkyl group, a cycloalkyl group, a substituted or unsubstituted heterocyclic ring containing N and/or P, an aryl group, including a halogenated aryl group And a substituted aryl group of an alkyl-substituted aryl group, such as an aminoalkyl group, a carboxyalkyl group, a phosphonic acid alkyl group, an alkylenimine group, a hydroxyalkyl group, a substituted alkyl group of a decane-substituted alkyl group, and the like.

膦酸酯可更特別選自具有按照II、III及IV之式之膦酸及膦酸酯，而膦酸酯(II)具有以下之式： 其中R1 為PO3 X2 或R2 PO3 X2 ，其中X2 獨立選自H或陽離子，且R2 為C1 －C5 伸烷基，較佳地為亞甲基。Z為選自H、鹵素、C1 －C5 烷基、NO2 、及COOH中之一員。較佳地，Z處於對位。此群之示範性成員包括4－溴苄膦酸，4－第三丁基苄膦酸，苯基膦酸，4－羥苄基膦酸，4－硝基苄基膦酸，4－甲基苄基膦酸，4－羧基苄基膦酸，及4－溴苄基膦酸乙酯。具有式(III)之膦酸酯亦可被提及 其中X如上文在調配物(I)中所定義且R3 為C1 －C5 烷基、C1 －C5 羧烷基、C1 －C5 膦酸基烷基、C1 －C5 矽烷氧基烷基、C1 －C5 亞胺基烷基及C1 －C5 膦亞胺烷基。此群之示範性成員包括2－羧乙基膦酸、膦酸三羥基矽烷丙基甲酯、1,2－二伸乙基二膦酸、亞胺基雙(甲基膦酸)及第三丁基膦酸。The phosphonates are more particularly selected from the group consisting of phosphonic acids and phosphonates of the formulas II, III and IV, while the phosphonates (II) have the formula: Wherein R 1 is PO 3 X 2 or R 2 PO 3 X 2 , wherein X 2 is independently selected from H or a cation, and R 2 is a C 1 -C 5 alkylene group, preferably a methylene group. Z is one member selected from the group consisting of H, halogen, C 1 -C 5 alkyl, NO 2 , and COOH. Preferably, Z is in the para position. Exemplary members of this group include 4-bromobenzylphosphonic acid, 4-tert-butylbenzylphosphonic acid, phenylphosphonic acid, 4-hydroxybenzylphosphonic acid, 4-nitrobenzylphosphonic acid, 4-methyl Benzylphosphonic acid, 4-carboxybenzylphosphonic acid, and ethyl 4-bromobenzylphosphonate. Phosphonates of formula (III) may also be mentioned Wherein X is as defined above in the formulation (I) and R 3 is C 1 -C 5 alkyl, C 1 -C 5 carboxyalkyl, C 1 -C 5 phosphonoalkyl, C 1 -C 5 a decyloxyalkyl group, a C 1 -C 5 iminoalkyl group, and a C 1 -C 5 phosphinimine alkyl group. Exemplary members of this group include 2-carboxyethylphosphonic acid, trihydroxydecylpropyl methyl phosphonate, 1,2-diethylidene diphosphonic acid, imino bis(methylphosphonic acid), and third Butylphosphonic acid.

膦酸酯亦可選自式IV。The phosphonate may also be selected from Formula IV.

其中X如在上式I中所定義。R4 及R5 獨立選自氫、C1 －C5 烷基、C1 －C5 羥烷基及C1 －C5 膦酸基烷基，限制條件為R4 及R5 可以共價鍵鍵結在一起形成環狀結構，R6 可存在或不存在，當存在時，其選自C1 －C5 伸烷基；Q為N或N氧化物(即N＝O＋ )。此群IV之示範性成員包括膦酸[[(2－羥乙基)亞胺基]雙(亞甲基)]雙－,N氧化物CAS 137006－87－2，本文稱為直鏈EBO；及[四氫－2－羥基－4H－1,4,2－氧氮磷－4－基]甲基]－N,P－二氧化物CAS 133839－05－01，本文稱作環狀EBO。 Wherein X is as defined in the above formula I. R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 5 alkyl, C 1 -C 5 hydroxyalkyl and C 1 -C 5 phosphonoalkyl, with the proviso that R 4 and R 5 may be covalently bonded. The bonds are bonded together to form a cyclic structure, R 6 may or may not be present, when present, it is selected from a C 1 -C 5 alkylene group; and Q is an N or N oxide (i.e., N = O + ). Exemplary members of this group IV include phosphonic acid [[(2-hydroxyethyl)imido]bis(methylene)] bis-, N-oxide CAS 137006-87-2, herein referred to as linear EBO; And [tetrahydro-2-hydroxy-4H-1,4,2-oxophosphorus 4-yl]methyl]-N,P-dioxide CAS 133839-05-01, referred to herein as cyclic EBO.

較佳地，直鏈EBO與環狀EBO同時以混合溶液之形式存在。基於初步資料，較佳地使用直鏈EBO及環狀EBO之混合物。此等膦酸酯可經由以下製備途徑被製備。Preferably, the linear EBO and the cyclic EBO are simultaneously present in the form of a mixed solution. Based on preliminary information, a mixture of linear EBO and cyclic EBO is preferably used. These phosphonates can be prepared via the following preparative routes.

膦酸酯製備：直鏈EBO及環狀EBO之混合物(群IV)向配備有機械攪拌器、溫度計、頂部冷凝器及加料孔之玻璃反應容器饋入70%亞磷酸水溶液(2.00莫耳)及32%鹽酸水溶液(0.33莫耳)。隨後邊攪拌邊向該酸溶液逐滴添加90%活性三聚甲醛(2.00莫耳)。添加後，在氮氣射流下將反應器內容物加熱至85±2℃並保持30分鐘。隨後在維持批料溫度為85±2℃的條件下，將氮氣射流切換為氮氣層並經1至2小時逐滴饋入99%單乙醇胺(1.00莫耳)。添加後，將該批料加熱至93±2℃並保持8小時。保持8小時之後冷卻該批料並藉由添加50%氫氧化鈉水溶液(3.73莫耳)將其pH值調節為9－10。接著將該批料溫度調節至40±2℃並逐滴饋入35%過氧化氫水溶液(1.07莫耳)經大約1小時並同時冷卻以維持該批料溫度在38－52℃之間。添加後，將該批料保持在50±2℃ 2小時。隨後冷卻該批料至室溫並加以收集。在冷卻期間，向該批料饋入50%葡萄糖酸水溶液(0.005莫耳)。Phosphonate preparation: a mixture of linear EBO and cyclic EBO (Group IV) was fed a 70% aqueous solution of phosphorous acid (2.00 mol) to a glass reaction vessel equipped with a mechanical stirrer, thermometer, overhead condenser and feed port. 32% aqueous hydrochloric acid (0.33 mol). Then 90% active trioxane (2.00 mole) was added dropwise to the acid solution with stirring. After the addition, the reactor contents were heated to 85 ± 2 ° C under a nitrogen stream for 30 minutes. The nitrogen jet was then switched to a nitrogen blanket while maintaining the batch temperature at 85 ± 2 °C and 99% monoethanolamine (1.00 mol) was fed dropwise over 1 to 2 hours. After the addition, the batch was heated to 93 ± 2 ° C for 8 hours. After 8 hours, the batch was cooled and its pH was adjusted to 9-10 by the addition of 50% aqueous sodium hydroxide (3.73 mol). The batch temperature was then adjusted to 40 ± 2 ° C and 35% aqueous hydrogen peroxide (1.07 moles) was fed dropwise over about 1 hour while cooling to maintain the batch temperature between 38-52 °C. After the addition, the batch was kept at 50 ± 2 ° C for 2 hours. The batch was then cooled to room temperature and collected. During the cooling, a 50% aqueous solution of gluconic acid (0.005 mol) was fed to the batch.

由13P NMR以直鏈EBO與環狀EBO之鈉鹽的標稱莫耳比為1：1來表徵所製得之產物，此產物下文統稱為EBO。此材料亦由痕量之殘餘亞磷酸、氧化副產物磷酸、及副產物亞甲基二膦酸的鈉鹽組成。本發明之一較佳實施例利用所製得的該產物而未經純化。The resulting product was characterized by 13P NMR with a nominal molar ratio of linear EBO to the sodium salt of cyclic EBO of 1:1. This product is hereinafter collectively referred to as EBO. This material also consists of traces of residual phosphorous acid, oxidation by-product phosphoric acid, and the sodium salt of the by-product methylene diphosphonic acid. A preferred embodiment of the invention utilizes the product produced without purification.

可如下製備其它示範性膦酸酯：膦酸酯製備：4－溴苄基膦酸(BBPA)(群II)將4－溴苄基溴(4.4 g，0.017 mol)與三乙基膦酸酯(3.5 g，3.5 mL，0.021 mol)結合並在130℃加熱12小時。將反應物冷卻至室溫並儲存於暗處。將中間物溶於20 mL之MeCN中並用固體KI(8.7 g，0.0525 mol)加以處理隨後用Me3 SiCl(5.63 g，6.6 mL，0.105 mol)加以處理。將反應物在60℃攪拌6小時再冷卻至室溫。過濾固體KCl，並將殘餘物蒸發至乾。取出殘餘物置於10 mL蒸餾水中。5分鐘後沉澱出琥珀油。過濾該固體並用冷己烷洗滌。此得到3.02 g(70%)白灰色粉末之產物。Other exemplary phosphonates can be prepared as follows: Phosphonate preparation: 4-bromobenzylphosphonic acid (BBPA) (Group II) 4-bromobenzyl bromide (4.4 g, 0.017 mol) with triethylphosphonate (3.5 g, 3.5 mL, 0.021 mol) was combined and heated at 130 °C for 12 hours. The reaction was cooled to room temperature and stored in the dark. Then it is treated with Me 3 SiCl (5.63 g, 6.6 mL, 0.105 mol) was dissolved in 20 mL intermediate of them MeCN and treated with solid KI (8.7 g, 0.0525 mol) . The reaction was stirred at 60 ° C for 6 hours and then cooled to room temperature. The solid KCl was filtered and the residue was evaporated to dry. The residue was taken out and placed in 10 mL of distilled water. Amber oil precipitated after 5 minutes. The solid was filtered and washed with cold hexanes. This gave the product as a 3.02 g (70%) white gray powder.

膦酸酯製備：4－第三丁苄基膦酸(TBBPA)(群II)將4－第三丁苄基溴(0.91 g，4.0 mmol)與三乙基膦酸酯(0.798 g，0.836 mL，4.8 mmol)結合並在130℃加熱24小時。將反應物冷卻至室溫並儲存於暗處。隨後將中間物溶於5 mL之MeCN中並用固體KI(1.92 g，11.62 mmol)加以處理隨後用Me3 SiCl(1.27 g，1.47 mL，11.62 mmol)加以處理。將反應物在60℃攪拌12小時再冷卻至室溫。過濾固體KCl，並將殘餘物蒸發至乾。取出殘餘物置於10 mL蒸餾水中。5分鐘後沉澱出琥珀油。過濾該固體並用冷己烷洗滌。此得到0.80 g(90%)淡黃色粉末之產物。Phosphonate preparation: 4-tert-butylbenzylphosphonic acid (TBBPA) (Group II) 4-tert-butylbenzyl bromide (0.91 g, 4.0 mmol) and triethylphosphonate (0.798 g, 0.836 mL, 4.8 mmol) Combine and heat at 130 ° C for 24 hours. The reaction was cooled to room temperature and stored in the dark. The intermediate was then dissolved then be treated with Me 3 SiCl (1.27 g, 1.47 mL, 11.62 mmol) 5 mL of MeCN and be treated with solid KI (1.92 g, 11.62 mmol) . The reaction was stirred at 60 ° C for 12 hours and then cooled to room temperature. The solid KCl was filtered and the residue was evaporated to dry. The residue was taken out and placed in 10 mL of distilled water. Amber oil precipitated after 5 minutes. The solid was filtered and washed with cold hexanes. This gave the product of 0.80 g (90%) of a pale yellow powder.

第II類之其它經取代之苄基膦酸酯以類似方式製備。即，使用相應的苄基溴作為初始反應物並隨後與三乙基膦酸反應以形成所要之經取代苄基膦酸酯。該酯可經由習知技術轉化為酸形式或以其此所製得之酯形式使用。Other substituted benzylphosphonates of Group II are prepared in a similar manner. That is, the corresponding benzyl bromide is used as the initial reactant and then reacted with triethylphosphonic acid to form the desired substituted benzylphosphonate. The ester can be converted to the acid form by conventional techniques or used in the form of the ester thus obtained.

所有其它具體列出的膦酸酯均為可購得的。All other specifically listed phosphonates are commercially available.

另外，該酸性處理組合物中可包括矽烷(d)。代表性矽烷包括但不限於，烷氧基矽烷、胺基矽烷、脲基矽烷、縮水甘油氧基矽烷、或其混合物。美國專利第6,203,854號明示了較佳的烷氧基矽烷及胺基矽烷。目前，最佳為購自GE Silicones－OSI的脲丙基三甲氧基矽烷，名稱為Silquest A 1524。Additionally, decane (d) may be included in the acidic treatment composition. Representative decanes include, but are not limited to, alkoxydecanes, amino decanes, ureido decanes, glycidoxy decanes, or mixtures thereof. Preferred alkoxydecanes and aminodecanes are shown in U.S. Patent No. 6,203,854. Currently, the most preferred is urea propyl trimethoxy decane available from GE Silicones-OSI under the name Silquest A 1524.

根據本發明之較佳酸性水性組合物為無鉻酸鹽並包括：a1)以超過其溶解限度約0.01 wt%至約10 wt%的量存在的鋯源；a2)以超過其溶解限度約0.01 wt%至約10 wt%的量存在的鈦源；b)氟化物源，其中氟化物以相對於所存在Zr與Ti之總莫耳數之過量莫耳數而存在，較佳地以所存在Zr與Ti之總莫耳數至少約4倍之過量莫耳數而存在；c)以約0.01－50 wt%之量存在的膦酸或膦酸酯；及視需要d)矽烷。The preferred acidic aqueous composition according to the present invention is chromate-free and comprises: a1) a zirconium source present in an amount in excess of its solubility limit of from about 0.01% to about 10% by weight; a2) in excess of its solubility limit of about 0.01 a source of titanium present in an amount from wt% to about 10 wt%; b) a source of fluoride wherein the fluoride is present in excess of the number of moles relative to the total number of moles of Zr and Ti present, preferably in the presence of The total molar number of Zr and Ti is present at least about 4 times the excess number of moles; c) the phosphonic acid or phosphonate present in an amount of from about 0.01 to 50% by weight; and optionally d) decane.

組合物之剩餘部份包含水及pH調節劑以調節pH於約0.5－6之範圍內。酸性水性組合物的重量為100 wt%。The remainder of the composition contains water and a pH adjusting agent to adjust the pH in the range of about 0.5-6. The weight of the acidic aqueous composition was 100 wt%.

本發明之一更具體之態樣中，水性組合物包含：1)0.01－40 wt%之量的H2 ZrF6 ；2)0.01－40 wt%之量的H2 TiF6 ；3)約0.01－50 wt%之量的膦酸或膦酸酯；4)約0.00－20 wt%之量的矽烷；剩餘部份之水及pH調節劑。組合物總量(包括水)為100 wt%。In a more specific aspect of the invention, the aqueous composition comprises: 1) H 2 ZrF 6 in an amount of 0.01-40 wt%; 2) H 2 TiF 6 in an amount of 0.01-40 wt%; 3) about 0.01 -50 wt% of phosphonic acid or phosphonate; 4) decane in an amount of about 0.00-20 wt%; the remainder of the water and pH adjuster. The total amount of the composition (including water) was 100 wt%.

較佳組合物包括：1)約0.01－40 wt%之量的H2 ZrF6 ；2)約0.01－40 wt%之量的H2 TiF6 ；3)選自由(i)直鏈EBO及(ii)環狀EBO及(i)與(ii)之混合物組成之群的膦酸或膦酸酯。此等膦酸酯以約0.01－50 wt%之組合量而存在。組合物之剩餘部份為以約0.00－20 wt%之量視需要之矽烷(4)、水及pH調節劑。Preferred compositions include: 1) H 2 ZrF 6 in an amount of from about 0.01 to 40 wt%; 2) H 2 TiF 6 in an amount of from about 0.01 to 40 wt%; 3) selected from (i) linear EBO and ( Ii) a phosphonic acid or phosphonate of the group consisting of a cyclic EBO and a mixture of (i) and (ii). These phosphonates are present in a combined amount of from about 0.01% to about 50% by weight. The remainder of the composition is decane (4), water and a pH adjusting agent in an amount of from about 0.00 to 20% by weight.

必要的金屬表面可藉由處理液以噴淋、浸沒、或其它應用形式接觸。處理液可加以沖洗並乾燥使得經製備之金屬表面準備好在其上塗覆乾燥塗層。The necessary metal surface can be contacted by spraying, immersion, or other application by the treatment fluid. The treatment liquid can be rinsed and dried so that the prepared metal surface is ready to be coated with a dry coating thereon.

將根據本發明之酸性水溶液或分散液塗覆至該金屬表面以在經處理之表面產生大於約每平方英尺1毫克的塗層重量，更佳地，重量為每平方英尺約2－500毫克。若用於商業應用中，則可使用包含約3－100 wt%、較佳為10－100 wt%濃度之以上調配物之工作液來接觸所要的金屬表面。An acidic aqueous solution or dispersion according to the present invention is applied to the metal surface to produce a coating weight of greater than about 1 milligram per square foot on the treated surface, and more preferably from about 2 to 500 milligrams per square foot. If used in commercial applications, a working fluid comprising a concentration of from about 3 to 100 wt%, preferably from 10 to 100 wt%, of the above formulation can be used to contact the desired metal surface.

如商業應用之慣例，調配物中可包括添加劑以促進該轉化塗層之形成。可添加諸如硝酸鹽、亞硝酸鹽、氯酸鹽、溴酸鹽及硝基芳族化合物之氧化劑以加快並維持塗層之形成。可添加無機或有機的酸與鹼以維持工作浴液之pH值。Additives may be included in the formulation to facilitate the formation of the conversion coating, as is customary in commercial applications. An oxidizing agent such as a nitrate, a nitrite, a chlorate, a bromate, and a nitroaromatic compound may be added to accelerate and maintain the formation of the coating. An inorganic or organic acid and base may be added to maintain the pH of the working bath.

實例Instance

現結合以下比較實例及工作實例對本發明加以說明。工作實例應視為本發明之特定實施例之說明而不應被認為是限制本發明之範疇。The invention will now be described in connection with the following comparative examples and working examples. The working examples are to be considered as illustrative of specific embodiments of the invention and should not be construed as limiting the scope of the invention.

比較實例1Comparative example 1

為確立基線效能，在不添加任何額外添加劑的情況下對鈦及鋯組分加以評估。To establish baseline performance, the titanium and zirconium components were evaluated without the addition of any additional additives.

一般預處理製程：使用ACT Laboratories冷軋鋼板。General pretreatment process: ACT Laboratories cold rolled steel plate was used.

用2%Betz Kleen 132(購自GE Water & Process Technologies)在140℉噴淋90秒進行清洗。Washing was carried out with 2% Betz Kleen 132 (available from GE Water & Process Technologies) at 140 °F for 90 seconds.

沖洗：應用自來水噴淋30秒預處理：在140℉浸沒2分鐘沖洗：去離子水灌沖30秒乾燥：熱風槍調配物： Flushing: Apply tap water spray for 30 seconds Pretreatment: immerse for 2 minutes at 140 °F Flush: DI water rinse for 30 seconds Dry: Heat gun formulation:

預處理之後，將板塗佈購自PPG Industries的單塗層聚酯油漆系統White Polycron III(AG452W3223)。根據廠商說明書塗覆油漆並加以固化。塗佈後，根據ASTM B－117使板經受168小時的中性鹽霧試驗(NSS)並根據ASTM D－1654(表1)評價劃線蠕變(creep from the scribe)。After pretreatment, the panels were coated with White Polycron III (AG452W3223), a one-coat polyester paint system available from PPG Industries. Paint was applied and cured according to the manufacturer's instructions. After coating, the panels were subjected to a 168 hour neutral salt spray test (NSS) according to ASTM B-117 and evaluated for creep from the scribe according to ASTM D-1654 (Table 1).

實例1Example 1

評估以下調配物以檢查向鹼性鈦＋鋯調配物添加膦酸酯的效果。如比較實例1之方式對板加以處理並塗佈。試驗結果包含於表2中。The following formulations were evaluated to check the effect of adding a phosphonate to an alkaline titanium + zirconium formulation. The panels were treated and coated as in Comparative Example 1. The test results are contained in Table 2.

所使用的縮寫：Ti(ioPr)4 ＝異丙醇鈦EBO＝經混合的直鏈與環狀EBO直鏈EBO＝膦酸[[(2－羥乙基)亞胺基]雙(亞甲基)]雙－,N氧化物環狀EBO＝膦酸[(四氫－2－羥基－4H－1,4,2－噁唑膦素－4－基)甲基]－N,P－二氧化物BBPA＝4－溴苄基膦酸CEPA＝2－羧乙基膦酸TEOS＝矽酸四乙酯GPTMS＝縮水甘油氧基丙基三甲氧基矽烷UPTMS＝脲基丙基三甲氧基矽烷TBBPA＝4－第三丁基苯膦酸EDPA＝1,2－伸乙基二膦酸THSPMP＝3－三羥基矽烷基丙基甲基膦酸酯Abbreviations used: Ti(ioPr) 4 = titanium isopropoxide EBO = mixed linear and cyclic EBO linear EBO = phosphonic acid [[(2-hydroxyethyl)imido] bis (methylene )] bis-, N-oxide cyclic EBO = phosphonic acid [(tetrahydro-2-hydroxy-4H-1,4,2-oxazoline-4-yl)methyl]-N,P-dioxide BBPA=4-bromobenzylphosphonic acid CEPA=2-carboxyethylphosphonic acid TEOS=tetraethyl phthalate GPTMS=glycidoxypropyltrimethoxydecane UPTMS=ureidopropyltrimethoxydecane TBBPA= 4-tert-butylphenylphosphonic acid EDPA=1,2-extended ethyldiphosphonic acid THSPMP=3-trihydroxydecylpropylmethylphosphonate

[B958/P60、B1000/P60及B958/P95板購自ACT Laboratories,Inc.] [B958/P60, B1000/P60 and B958/P95 boards were purchased from ACT Laboratories, Inc.]

實例2Example 2

如比較實例1之方法製備並塗佈以下額外調配物： The following additional formulations were prepared and coated as in Comparative Example 1:

所使用的縮寫詞與實例1中相向，另外PPA＝苯基膦酸。The abbreviations used were the same as in Example 1, and additionally PPA = phenylphosphonic acid.

如實例1中所敍述之方法進行根據ASTM B－117及D－1654之中性鹽霧試驗。結果記錄於表3。The neutral salt spray test according to ASTM B-117 and D-1654 was carried out as described in Example 1. The results are reported in Table 3.

實例3Example 3

如實例1之方法評估額外膦酸酯。按照以下描述製備Ti與Zr組分之鹼性調配物：鹼性調配物： Additional phosphonates were evaluated as in Example 1. A basic formulation of the Ti and Zr components was prepared as follows: Basic formulation:

中性鹽霧結果在表4中給出。Neutral salt spray results are given in Table 4.

實例4Example 4

為進一步評估本發明之效能，製備並試驗以下調配物。製備並使用各組合物之多份浴液以便可製成多個複製品。NSS結果為穿過各組合物之二十塊板的平均值。如實例1之方法處理鋼板。To further evaluate the efficacy of the present invention, the following formulations were prepared and tested. Multiple portions of the bath of each composition are prepared and used so that multiple copies can be made. The NSS results are the average of twenty plates passing through each composition. The steel sheet was treated as in Example 1.

實例5Example 5

為說明氧化劑及pH調節劑之用途，製備以下實例。To illustrate the use of oxidizing agents and pH adjusting agents, the following examples were prepared.

藉由以下製程順序製備購自ACT Laboratories之CRS板：在140℉下、在鹼性清洗劑(Kleen 132)中清洗60秒用水沖洗15秒處理一在120℉及10 psi噴淋塗覆30秒用去離子水沖洗10秒熱空氣乾燥 CRS plates purchased from ACT Laboratories were prepared by the following process sequence: washing at 140 °F in alkaline cleaner (Kleen 132) for 60 seconds with water for 15 seconds, treatment at 120 °F and 10 psi for 30 seconds Rinse with deionized water for 10 seconds hot air drying

將板塗佈Polycron油漆並於240小時中性鹽霧暴露評估效能。The plates were coated with Polycron paint and evaluated for efficacy at 240 hours of neutral salt spray exposure.

儘管本發明已關於特定實施例進行描述，但是顯然本發明之諸多其它形式及修改對於熟習此項技術者顯而易見。所附申請專利範圍及本發明通常被理解為涵蓋在本發明之真正精神及範疇內的所有該等各種形式及修改。While the invention has been described with respect to the specific embodiments, it will be The scope of the appended claims and the invention are intended to be construed as

Claims (13)

一種塗佈一金屬或金屬合金表面之方法，其包含將該表面與一有效量之無鉻酸鹽水性處理溶液或分散液接觸，該處理溶液或分散液包含(a)包含一或多個選自IV B族元素的一或多種材料；(b)氟化物，(c)膦酸或膦酸酯；其中該膦酸或膦酸酯(c)係選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群，且其中該膦酸或膦酸酯(c)以約0.01-50 wt%之量存在。 A method of coating a surface of a metal or metal alloy comprising contacting the surface with an effective amount of a chromate-free aqueous treatment solution or dispersion comprising (a) comprising one or more selected One or more materials from Group IV B elements; (b) fluoride, (c) phosphonic acid or phosphonate; wherein the phosphonic acid or phosphonate (c) is selected from the group consisting of phosphonic acid [[(2-hydroxyethyl) Imino] bis(methylene)] bis-, N-oxide (linear EBO), phosphonic acid [(tetrahydro-2-hydroxy-4H-1,4,2-oxazophos-4) a group consisting of methyl]-N,P-dioxide (cyclic EBO) and mixtures thereof, and wherein the phosphonic acid or phosphonate (c) is present in an amount of from about 0.01% to about 50% by weight. 如請求項1之方法，其中(a)包含H2 ZrF6 及H2 TiF6 。The method of claim 1, wherein (a) comprises H 2 ZrF 6 and H 2 TiF 6 . 如請求項1之方法，其中該溶液或分散液進一步包含至少再一膦酸或膦酸酯。 The method of claim 1, wherein the solution or dispersion further comprises at least one additional phosphonic acid or phosphonate. 如請求項3之方法，其中該至少再一膦酸或膦酸酯係選自由式II、III或IV組成之群，其中式II具有結構： 其中R1 為PO3 X2 或R2 PO3 X2 ，其中X2 為陽離子或H；R2 為C1 -C5 伸烷基且Z為選自H、鹵素、C1 -C5 烷基、NO2 、及 COOH中之一員；式III具有結構： 其中X獨立選自陽離子或H；且R3 為C1 -C5 烷基、C1 -C5 羧烷基、C1 -C5 膦酸基烷基、C1 -C5 矽烷氧基烷基、及C1 -C5 亞胺基烷基或C1 -C5 膦酸基亞胺基烷基；及式IV具有結構： 其中X如上文所定義；R4 及R5 獨立選自H、C1 -C5 烷基、C1 -C5 羥烷基及C1 -C5 膦酸基烷基，限制條件為R4 與R5 可以共價鍵鍵結在一起形成環狀結構；R6 可存在或不存在，且當存在時為C1 -C5 伸烷基部分；且Q為N或N氧化物+ 。The method of claim 3, wherein the at least one further phosphonic acid or phosphonate is selected from the group consisting of Formula II, III or IV, wherein Formula II has the structure: Wherein R 1 is PO 3 X 2 or R 2 PO 3 X 2 , wherein X 2 is a cation or H; R 2 is a C 1 -C 5 alkylene group and Z is selected from the group consisting of H, halogen, C 1 -C 5 alkane One of the base, NO 2 , and COOH; Formula III has the structure: Wherein X is independently selected from cation or H; and R 3 is C 1 -C 5 alkyl, C 1 -C 5 carboxyalkyl, C 1 -C 5 phosphoalkylalkyl, C 1 -C 5 decyloxyalkane a group, and a C 1 -C 5 iminoalkyl group or a C 1 -C 5 phospho acid iminoalkyl group; and the formula IV has the structure: Wherein X is as defined above; R 4 and R 5 are independently selected from H, C 1 -C 5 alkyl, C 1 -C 5 hydroxyalkyl and C 1 -C 5 phosphonoalkyl, with the limitation R 4 R 5 may be covalently bonded together to form a cyclic structure; R 6 may or may not be present, and when present, is a C 1 -C 5 alkyl moiety; and Q is N or N oxide + . 如請求項4之方法，其中該至少再一膦酸或膦酸酯係選自式(II)。 The method of claim 4, wherein the at least one additional phosphonic acid or phosphonate is selected from the group consisting of formula (II). 如請求項5之方法，其中該至少再一膦酸或膦酸酯係選 自以下各物組成之群之一或多個成員：4-溴苄基膦酸，4-第三丁基苄基膦酸，苯基膦酸，4-羥苄基膦酸，4-硝基苄基膦酸，4-甲基苄基膦酸，4-羧基苄基膦酸及4-溴苄基膦酸乙酯。 The method of claim 5, wherein the at least one phosphonic acid or phosphonate is selected One or more members of the group consisting of: 4-bromobenzylphosphonic acid, 4-tert-butylbenzylphosphonic acid, phenylphosphonic acid, 4-hydroxybenzylphosphonic acid, 4-nitro Benzylphosphonic acid, 4-methylbenzylphosphonic acid, 4-carboxybenzylphosphonic acid and ethyl 4-bromobenzylphosphonate. 一種用於在金屬表面上形成一轉化或鈍化塗層之酸性、水性組合物或分散液，該組合物不含鉻酸鹽並包含(a)包含一或多個選自IV B族元素的一或多種材料；(b)氟化物；及(c)膦酸或膦酸酯；其中該膦酸或膦酸酯(c)係選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群，且其中該膦酸或膦酸酯以約0.01-50 wt%之量存在。 An acidic, aqueous composition or dispersion for forming a conversion or passivation coating on a metal surface, the composition being free of chromate and comprising (a) one or more selected from the group consisting of Group IV B elements Or a plurality of materials; (b) fluoride; and (c) a phosphonic acid or phosphonate; wherein the phosphonic acid or phosphonate (c) is selected from the group consisting of phosphonic acid [[(2-hydroxyethyl)imido] Bis(methylene)]bis-, N-oxide (linear EBO), phosphonic acid [(tetrahydro-2-hydroxy-4H-1,4,2-oxazoline-4-yl)methyl] a group of -N,P-dioxide (cyclic EBO) and mixtures thereof, and wherein the phosphonic acid or phosphonate is present in an amount of from about 0.01% to about 50% by weight. 如請求項7之組合物，其中(a)包含H2 ZrF6 及H2 TiF6 。The composition of claim 7, wherein (a) comprises H 2 ZrF 6 and H 2 TiF 6 . 如請求項7之組合物，其中該組合物進一步包含至少再一膦酸或膦酸酯。 The composition of claim 7, wherein the composition further comprises at least one additional phosphonic acid or phosphonate. 如請求項9之組合物，其中該至少再一膦酸或膦酸酯係選自由式II、III或IV組成之群，其中式II具有結構： 其中R1 為PO3 X2 或R2 PO3 X2 ，其中X2 為陽離子或H；R2 為C1 -C5 伸烷基且Z為選自H、鹵素、C1 -C5 烷基、NO2 、及COOH中之一員；式III具有結構： 其中X獨立選自陽離子或H；且R3 為C1 -C5 烷基、C1 -C5 羧烷基、C1 -C5 膦酸基烷基、C1 -C5 矽烷氧基烷基、及C1 -C5 亞胺基烷基或C1 -C5 膦酸基亞胺基烷基；及式IV具有結構： 其中X如上文所定義；R4 及R5 獨立選自H、C1 -C5 烷基、C1 -C5 羥烷基及C1 -C5 膦酸基烷基，限制條件為R4 與R5 可以共價鍵鍵結在一起形成環狀結構；R6 可存在或不存在，且當存在時為C1 -C5 伸烷基部分；且Q為N或N氧化物+ 。The composition of claim 9, wherein the at least one phosphonic acid or phosphonate is selected from the group consisting of Formula II, III or IV, wherein Formula II has the structure: Wherein R 1 is PO 3 X 2 or R 2 PO 3 X 2 , wherein X 2 is a cation or H; R 2 is a C 1 -C 5 alkylene group and Z is selected from the group consisting of H, halogen, C 1 -C 5 alkane One of the base, NO 2 , and COOH; Formula III has the structure: Wherein X is independently selected from cation or H; and R 3 is C 1 -C 5 alkyl, C 1 -C 5 carboxyalkyl, C 1 -C 5 phosphoalkylalkyl, C 1 -C 5 decyloxyalkane a group, and a C 1 -C 5 iminoalkyl group or a C 1 -C 5 phospho acid iminoalkyl group; and the formula IV has the structure: Wherein X is as defined above; R 4 and R 5 are independently selected from H, C 1 -C 5 alkyl, C 1 -C 5 hydroxyalkyl and C 1 -C 5 phosphonoalkyl, with the limitation R 4 R 5 may be covalently bonded together to form a cyclic structure; R 6 may or may not be present, and when present, is a C 1 -C 5 alkyl moiety; and Q is N or N oxide + . 如請求項10之組合物，其中該至少再一膦酸或磷酸酯係 選自式II。 The composition of claim 10, wherein the at least one phosphonic acid or phosphate system Selected from Formula II. 如請求項11之組合物，其中該至少再一膦酸或膦酸酯係選自由以下各物組成之群：4-溴苄基膦酸、4-第三丁基苄基膦酸、苯基膦酸，4-羥基苄基膦酸，4-硝基苄基膦酸，4-甲基苄基膦酸，4-羧基苄基膦酸及4-溴苄基膦酸乙酯。 The composition of claim 11, wherein the at least one phosphonic acid or phosphonate is selected from the group consisting of 4-bromobenzylphosphonic acid, 4-tert-butylbenzylphosphonic acid, phenyl Phosphonic acid, 4-hydroxybenzylphosphonic acid, 4-nitrobenzylphosphonic acid, 4-methylbenzylphosphonic acid, 4-carboxybenzylphosphonic acid and ethyl 4-bromobenzylphosphonate. 一種在金屬表面上形成一轉化或鈍化塗層之組合物，該組合物包含以下物質之酸性水溶液或分散液：1)0.01-40 wt%之量的H2 ZrF6 ；2)0.01-40 wt%之量的H2 TiF6 ；3)選自由膦酸[[(2-羥乙基)亞胺基]雙(亞甲基)]雙-,N氧化物(直鏈EBO)、膦酸[(四氫-2-羥基-4H-1,4,2-噁唑膦素-4-基)甲基]-N,P-二氧化物(環狀EBO)及其混合物所組成之群之膦酸或膦酸酯；該膦酸或膦酸酯3)以約0.01-50 wt%之量存在，pH調節劑4)，約0.00-20 wt%之量的矽烷5)，剩餘部份之水，以等於100 wt%。A composition for forming a conversion or passivation coating on a metal surface, the composition comprising an acidic aqueous solution or dispersion of: 1) H 2 ZrF 6 in an amount of 0.01-40 wt%; 2) 0.01-40 wt. % of H 2 TiF 6 ; 3) selected from phosphonic acid [[(2-hydroxyethyl)imido]bis(methylene)] bis-, N-oxide (linear EBO), phosphonic acid [ Phosphine consisting of (tetrahydro-2-hydroxy-4H-1,4,2-oxazoline-4-yl)methyl]-N,P-dioxide (cyclic EBO) and mixtures thereof Acid or phosphonate; the phosphonic acid or phosphonate 3) is present in an amount of from about 0.01% to about 50% by weight, pH adjuster 4), decane in an amount of from about 0.00% to about 20% by weight, and the balance of water To equal 100 wt%.
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